EP0862548A1 - Method for the development of delta-lactones and hydroxy acids from unsaturated fatty acids and their clycerides - Google Patents
Method for the development of delta-lactones and hydroxy acids from unsaturated fatty acids and their clyceridesInfo
- Publication number
- EP0862548A1 EP0862548A1 EP96933182A EP96933182A EP0862548A1 EP 0862548 A1 EP0862548 A1 EP 0862548A1 EP 96933182 A EP96933182 A EP 96933182A EP 96933182 A EP96933182 A EP 96933182A EP 0862548 A1 EP0862548 A1 EP 0862548A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acids
- acid
- solvent
- lactones
- lactone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Definitions
- This invention relates to a novel process for producing ⁇ - lactones and 5-hydroxy fatty acids from unsaturated fatty acids and their glycerides.
- Gamma stearolactones and other small chain ⁇ -lactones have been used as greases, antioxidants, perfumes, food flavors and dispersants for motor fuels. Techniques for the synthesis of both ⁇ - and ⁇ -lactones have been described throughout the chemical literature, and have included acid catalyzed reactions of unsaturated or olefinic acids.
- Burg et al . (U.S. patent 5,380,894, issued January 10, 1995) disclosed a process for the production of estolides from ⁇ s and other unsaturated fatty acids in the presence of water and a clay catalyst. Burg et al . further disclosed hydrolyzing the estolides to form hydroxy fatty acids.
- Hydroxy fatty acids have been described, and are useful as lubricants and greases, and in cosmetics, soaps, detergents, and fabric softeners. However, there is no domestic commercial source of hydroxy fatty acids currently available. The hydroxy fatty acids are commonly derived from castor oil which must be imported.
- the ⁇ -lactones may be produced by reacting one or more ⁇ 5 or ⁇ 6 unsaturated fatty acids in the presence of an acid, clay or zeolite catalyst.
- the unsaturated fatty acids may be esterified with glycerol, and that the ⁇ -lactones may be produced by reacting mono-, di- or triglycerides of ⁇ 5 or ⁇ 6 unsaturated fatty acids with the same catalysts. Because the ⁇ -lactones may be produced from the triglycerides of unsaturated fatty acids, the instant process may be practiced using naturally occurring plant oils directly, without the need for any preliminary steps of saponification or steam splitting.
- the ⁇ -lactones so formed may be further reacted to produce 5-hydroxy fatty acids.
- These 5-hydroxy fatty acids may be produced by reaction of the ⁇ -lactones with an alkali in an aqueous solution.
- ⁇ -lactones and 5- hydroxy fatty acids may be formed from ⁇ 5 and ⁇ 6 unsaturated fatty acids.
- Preferred starting materials include but are not limited to free and esterified unsaturated fatty acids of the formula (I) :
- Ri-CH CH-fCH a -COORj (I) wherein n is 3 or 4, R, is hydrocarbon, particularly a C 4 to C 20 hydrocarbon, which may be saturated or unsaturated, and branched or straight chain, and R 2 is an H or a glyceride moiety which in combination with the fatty acid comprises a mono-, di- or triglyceride.
- Examples of particularly preferred unsaturated fatty acids which may be used herein include free and esterified 5-eicosenoic acid (20:1 ⁇ 5 ) , 5-docosenoic acid (22:1 ⁇ 5 ), 5,13-docosadienoic acid (22:2, ⁇ 5 ' 13 ), petroselinic acid (16:1 ⁇ 6 ), 18:1 ⁇ 5 fatty acids, 18:2 ⁇ 5 ' 9 fatty acids, 18:3 ⁇ 5 ' 9 ' 12 fatty acids, 20:3 ⁇ 5 ' 11 ' 14 fatty acids, and 20:4 A 5 ' 11 ' 14 ' 17 fatty acids.
- the ⁇ 5 and ⁇ * unsaturated fatty acids are naturally occurring in a variety of plant oils and may be conveniently obtained for use therefrom.
- Meadowfoam oil having a high content of ⁇ 5 unsaturated fatty acids (total fatty acids composed of approximately 60% 5-eicosenoic acid, 10% 5-docosenoic acid, 19% 5,13-docosadienoic acid, and less than 5% 18:1 ⁇ 5 fatty acids), is particularly preferred as a source of the starting material.
- oils which may be used as sources include pine oils (containing 18:1 ⁇ 5 , 18:2 ⁇ s ' 9 , 18:3 ⁇ 5 ' 9 ' 12 , 20:3 ⁇ 5 ' 11 ' 14 , and 20:4
- Suitable solvents for use herein include but are not limited to CH 2 C1 2 , CHC1 3 , hydrocarbons such as hexane and cyclohexane, and t-butanol, with CH 2 C1 2 being preferred.
- the volume of the solvent used may also significantly effect the ratio of ⁇ - to ⁇ -lactones in the product, with increased amounts of solvent relative to the unsaturated fatty acid generally providing greater ⁇ / ⁇ ratios.
- the actual volume of solvent will vary with the particular solvent selected, the starting fatty acids and reaction conditions, and may be determined by a practitioner skilled in the art. However, in the preferred embodiment using CH 2 C1 2 , the volume of solvent should be greater than or equal to about 100%, most preferably at least about 500% (wherein the solvent is measured as wt %) .
- reaction yields of ⁇ -lactones greater than 50% have been readily obtained, with yields from meadowfoam oil or its free fatty acids ranging from 70 to 90% after reaction for 24 hours.
- the resultant ⁇ -lactones may be represented by the general formula (II) : i o ,
- the ⁇ -lactones so-produced may be used as an emollient in cosmetics and moisturizing creams. It is also envisioned that, as with the ⁇ -lactones, the ⁇ -lactones will be useful as biodegradable lubricants and greases, antioxidants, perfumes, food flavors and dispersants for motor fuels. In addition to these direct applications, the ⁇ -lactones may also be used as intermediates for the production of other commercially valuable compounds, including but not limited to 5-hydroxy wax esters, 5-hydroxy amides including ethanolamide derivatives, and particularly 5-hydroxy fatty acids.
- Production of 5-hydroxy fatty acids may be readily accomplished by reaction of the ⁇ -lactones in the presence of an alkali in an aqueous solution.
- the ⁇ - lactones may be isolated prior to this reaction, in the alternative the reaction may be performed directly upon the reaction mixture resulting from ⁇ -lactone formation, thereby obviating any intermediate steps of separation and purification of the ⁇ -lactones.
- an aqueous solution of an alkali may be added and the reaction mixture held under conditions effective to form hydroxy fatty acids.
- the particular alkali employed is not critical, and virtually any hydroxy moiety containing base will be operable.
- Preferred alkali for use herein include alkali metal hydroxides such as KOH and NaOH. The amount of alkali added should be approximately 1.5 moles in excess beyond the amount required to neutralize any acid catalyst remaining from the initial reaction.
- Vacuum filtration provides the hydroxy fatty acids in greater than 70% yield.
- the ethyl acetate extraction step may be avoided by direct filtration of the pH adjusted solution. Recovery in this manner will provide a higher yield of a slightly less pure fraction of hydroxy fatty acids.
- the resultant 5-hydroxy fatty acids may be represented by the general formula (III):
- These hydroxy fatty acids may be used as biodegradable lubricants and greases, and in cosmetics, soaps, detergents, and fabric softeners.
- this reaction may also be conducted using either ⁇ -lactone which has been isolated or which remains in the initial reaction mixture.
- Catalysts and conditions for production of hydroxy wax esters are similar to those described for the production of the ⁇ -lactones.
- Suitable catalysts include, for example, mineral acids, lewis acids, clays and zeolites, with mineral acids such as H 2 S0 4 and p-toluene sulfonic acid being preferred.
- the temperature for the reaction is not critical and may vary between about 20 to 150°C. Interestingly, when the reaction is conducted at higher temperatures, the amount of catalyst may be reduced or the catalyst may even be entirely omitted.
- the 5-hydroxy wax esters are synthesized by mixing a slight excess of primary alcohol in the presence of about 0.01 equivalents of acid catalyst with ⁇ - lactone (at the melting point of the lactone) and mixed thoroughly. An immediate precipitate will form and the whole reaction will solidify within about 15 minutes. At this point the reaction may be diluted in hexane and vacuum filtered to give near quantitative conversion of the ⁇ -lactone to 5-hydroxy wax ester. Secondary, tertiary, hindered and other weaker nucleophilic alcohols will require longer reaction times and may not provide solid products.
- Hydroxy wax esters produced in accordance with this invention may be used as moisturizers in cosmetics, biodegradable lubricants and dispersing agents for pigments and dyes in inks. Furthermore, the compounds possess strong surface active or chelating properties permitting their use as detergents and floculants for heavy metals.
- the ⁇ -lactones may also be used to produce 5-hydroxy amides.
- the production of these compounds requires no catalyst to promote the reaction. Conversion takes place by mixing the ⁇ -lactone with a slight excess of amine at the melting point of the ⁇ -lactone.
- Primary amines provide an immediate precipitate upon addition of the amine signaling the completion of the reaction.
- Secondary, hindered and other weaker nucleophilic amines such as diethanol amine may require extended reaction times to reach completion.
- the reaction mixture Upon consumption of the lactone, the reaction mixture may be diluted in hexane and vacuum filtered to remove any excess amine. This reaction may yield a near quantitative conversion to the 5-hydroxy amines.
- Example 2 To examine the effects of different solvent concentrations on yields and ⁇ / ⁇ ratios, the reaction of Example 1 was repeated using CH 2 C1 2 (2.171 molal) as solvent, 2 molar equivalents of HC10 4 as catalyst and a temperature of 35°C with reflux for 3 hours. The results are shown in Table 2.
- Example 2 using 500% CH 2 C1 2 , except that 102g of meadowfoam oil was initially used (with the amounts of catalyst and solvent increased accordingly) .
- the reaction mixture containing the ⁇ - lactones was cooled to room temperature and a Dean-Stark trap placed on the flask.
- 43g of KOH dissolved in 500 ml of water was added slowly to the flask and then the solvent removed as the reaction warmed to 80°C. Ethanol was added in 10 ml portions to minimize foaming.
- the reaction was quenched by cooling in an ice-bath and adding cold acetic acid solution (19.3g in 500 ml H 2 0) to the flask with vigorous stirring. Vacuum filtration and recrystallization from ethyl acetate gave 73% isolated mass yield of 5-hydroxy fatty acids as determined by mass balance.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US534810 | 1990-06-05 | ||
US08/534,810 US5849935A (en) | 1995-09-27 | 1995-09-27 | Method for the development of δ-lactones and hydroxy acids from unsaturated fatty acids and their glycerides |
PCT/US1996/015603 WO1997011932A1 (en) | 1995-09-27 | 1996-09-27 | Method for the development of delta-lactones and hydroxy acids from unsaturated fatty acids and their clycerides |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0862548A1 true EP0862548A1 (en) | 1998-09-09 |
EP0862548A4 EP0862548A4 (en) | 1999-04-21 |
EP0862548B1 EP0862548B1 (en) | 2003-04-02 |
Family
ID=24131622
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96933182A Expired - Lifetime EP0862548B1 (en) | 1995-09-27 | 1996-09-27 | Method for the development of delta-lactones and hydroxy acids from unsaturated fatty acids and their clycerides |
Country Status (7)
Country | Link |
---|---|
US (1) | US5849935A (en) |
EP (1) | EP0862548B1 (en) |
AT (1) | ATE236113T1 (en) |
AU (1) | AU719911B2 (en) |
DE (1) | DE69627178T2 (en) |
NZ (1) | NZ319472A (en) |
WO (1) | WO1997011932A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7615231B2 (en) | 2005-10-24 | 2009-11-10 | Fan Tech, Ltd. | Methods for enhancing the morphology, tone, texture and/or appearance of skin or hair using a meadowlactone |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3054804A (en) * | 1961-02-21 | 1962-09-18 | Swern Daniel | Method for preparing gamma-stearolactone |
US5380894A (en) * | 1991-03-01 | 1995-01-10 | The United States Of America As Represented By The Secretary Of Agriculture | Production of hydroxy fatty acids and estolide intermediates |
-
1995
- 1995-09-27 US US08/534,810 patent/US5849935A/en not_active Expired - Lifetime
- 1995-09-27 NZ NZ319472A patent/NZ319472A/en not_active IP Right Cessation
-
1996
- 1996-09-27 DE DE69627178T patent/DE69627178T2/en not_active Expired - Lifetime
- 1996-09-27 AT AT96933182T patent/ATE236113T1/en not_active IP Right Cessation
- 1996-09-27 EP EP96933182A patent/EP0862548B1/en not_active Expired - Lifetime
- 1996-09-27 AU AU72010/96A patent/AU719911B2/en not_active Expired
- 1996-09-27 WO PCT/US1996/015603 patent/WO1997011932A1/en active IP Right Grant
Non-Patent Citations (2)
Title |
---|
No further relevant documents disclosed * |
See also references of WO9711932A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69627178D1 (en) | 2003-05-08 |
ATE236113T1 (en) | 2003-04-15 |
NZ319472A (en) | 1998-10-28 |
EP0862548A4 (en) | 1999-04-21 |
DE69627178T2 (en) | 2004-01-29 |
EP0862548B1 (en) | 2003-04-02 |
US5849935A (en) | 1998-12-15 |
AU719911B2 (en) | 2000-05-18 |
AU7201096A (en) | 1997-04-17 |
WO1997011932A1 (en) | 1997-04-03 |
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